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Bronsted-Lowry definition:
Acid is a substance that donates a proton.
Base is a substance that accepts a proton.
Conjugate acid: product that results when a base gains a proton.
Conjugate base: product that results when an acid loses a proton.
Examples:
2 H2O
H2O H Cl H3O Cl
base acid conjugate acid conjugate base
hydronium is chloride is
weaker acid than HCl weaker base than H2O
The stronger the acid, the weaker its conjugate base.
The conjugate base of a strong acid is a weak (stable) base.
The conjugate base of a weak acid is a strong base.
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There are weaker acids than H3O+? Yes!!!
The acidity increases from the top to the bottom due to increased
polarizability (ability to deform the electron density in the atom).
Larger atoms polarize easier because the valence electrons () are
farther away from the nucleus ().
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Order of Acidity
CH4 NH3 H 2O HF
pKa = 50 pKa = 36 pKa = 15.7 pKa = 3.2
H2Te HI
pKa = 2.6 pKa = 10
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The second factor in importance deals with Induction,
specifically Electron withdrawing effect. Induction is the
shifting of electrons in a bond as a result of the electronegativity
of nearby atoms.
For instance:
O
CH4 CH3Cl CH3SCH3 CH3CN
pKa = 50 pKa = 43 (aprox) pKa = 35 pKa = 25
O O O
CH3CCH3 CH3NO2 CH3CCH2CCH3
pKa = 20 pKa = 10 pKa = 9
O
CH3SH CH3OH CH3COH
pKa = 10.4 pKa = 15 pKa = 4.8
O O O O
ICH2COH BrCH2COH ClCH2COH FCH2COH
pKa = 3.15 pKa = 2.86 pKa = 2.81 pKa = 2.66
O O
Cl2CHCOH Cl3CCOH
pKa = 1.29 pKa = 0.65
O O O
ClCH2CH2CH2COH CH3CHCH2COH CH3CH2CHCOH
Cl Cl
pKa = 4.52 pKa = 4.06 pKa = 2.84
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The third factor in importance is the Resonance.
For instance:
Resonance stabilizes the conjugate base
OH O O O O
pKa = 10
OH O
pKa = 18
CH3CH2 CH2 CH CH C
the stronger the acid the weaker its conjuate base and viceversa
2 CF3SO3H CF3SO3
10 HI I
9 HBr Br
7 HCl Cl
2 CH3SO3H CH3SO3
1.7 H3O+ H2O
2.8 ClCH2CO2H ClCH2CO2
3.2 HF F
4.8 CH3CO2H CH3CO2
10 OH O
15 CH3OH CH3O
15.7 H2O HO
25 CH CH CH C
35 H2 H
36 NH3 H2N
40 CH3NH2 CH3NH
44 CH2 CH2 CH2 CH
50 CH3CH3 CH3CH2
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Arrange the following compounds in order of decreasing acidity
(strongest first).
NH2 - OH - SH - CH3- I-
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Lewis Acids and Bases
Cl CH3 O
Al C C
Cl Cl CH3 CH3 H H
H2O Br Br OH HS I Cl
(CH3)3P O e- CH C O H
CH3CCH3 CH3CO
CH3SCH3 C N (CH3)2N
For example:
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H2S + BF3 H2SBF3
Lewis Base Lewis Acid Complex
Nucleophile Electrophile
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